Willy bein



(No Model.)

W. BEIN.

PROGESS OF AND APPARATUS FOR ELEGTROLYZING;

No. 591,730. Patented Oct. 12,1897.

l l l l I' ll lall I ifi'inesses UNITED STATES PATENT OFFICE.

\VILLY BEIN, OF BERLIN, GERMANY.

PROCESS OF AND APPARATUS FOR ELECTROLYZING.

SPECIFICATION forming part of Letters Patent N 0. 591,730, dated October 1897- Application fil d June 15, 1896. Serial No. 595,681.

land November 12, 1894, No. 21,838; in I'ranoe July 20,1895,

(No model.) Patented in Germany October 22, 1893, No. 84,547; in Eng- I No. 236,203; in Belgium July 20,1895, N0.116,623; in

Hungary October 31,1895, No. 4,129, and in'Austria May 8, 1896,11'0. 1,812/16.

To all whom it may concern.-

Be it known that I, WILLY BEIN, doctor of philosophy, a subject of the King of Prussia, German Emperor, and a resident of Berlin, in the Kingdom of Prussia, German Empire, have invented a certain new and useful Improved Process of and Apparatus for Electrolyzing, (for which I have obtained patents in Germany, No. 84,547, dated October 22, 1893 in France, No. 236,203, dated July 520, 1895;

in Belgium, No. 116,623, dated July 20, 1895; in Austria, No; 1,812/ 16, dated May 8, 1896; in Hungary, No. 4,129, dated October 31, 1895, and in England, No. 21,838, dated November 12, 1894,) of which the following is a full, clear, and exact description.

If an electrolytic solution is electrolyzed for a considerable timein a cell, the products of decomposition will finally gather at the anode and cathode, and after this has taken place the electric energy conveyed to the solution will be lost. These products of decomposition have hitherto been separated by mechanical means-such as porous diaphragms, artificial or natural membranes, or the likein the case of standing electrolytes. The employment of diaphragms has many advantages. In the first place, theydo not entirely prevent a recombination of the products formed due to endosmotic action, as pointed out by Hittorf in Poggendorfi s Annale'n. Then, again, diaphragms produce considerable resistance and render it difficult to work with simple apparatus, they are not economical, and are subject to chemical and mechanical destruction.

In the electrolytic processes hitherto employed diaphragms have invariablybeen employed in order to enable the electrodes to be arranged as close together as possible and thus to reduce the resistance, but in the bestknown processes-- such, for instance, as that patented to Carmichael, No. 518,710, and in fact in all processes hitherto employed-the electrodes have been arranged one above the other, thus necessitating the employment of a diaphragm and involving the disadvantage that any gases which may be produced will pass through or cross the electrolytic path and cause the products of decomposition to rise into the neutral layer which intervenes between the electrodes.

According to the present invention the diaphragm is dispensed with entirely, a neutral layer or zone of the electrolytic solution being preserved and caused to act to keep the products of decomposition collecting at the electrodes separated. This neutral zone is obtained and preserved by arranging the electrodes one alongside of the other instead of one above the other. The electrodes may be arranged in one and the same horizontal plane or in varying horizontal planes or in planes substantially horizontal, the main condition being that they are arranged relatively sidewardly of each other. The relative vertical position of the electrodes with regard to each other depends upon the kind of salt to be decomposed, said electrodes being under all circumstances so arranged as to allow the gases, if such are produced, free exit without crossing'the path of the electric current.

I have found by numerous experiments that while the current is passing through the solution no practically-observable intermingling of the products of decomposition collecting at the electrodes takes place and that this is the case even in the presence of slight mechanical disturbances. The separating layer or zone of non-decomposed solution will gradually decrease in bulk the longer the process is continued, but no intermingling will take place. It will'thus be clear that if fresh solution is introduced into the neutral or non-decomposed zone in proportion to that removed by decomposition this zone will remain constant and form a fluid-diaphragm which will serve all practical purposes and obviate the necessity of a mechanical diaphragm.

Solution is drawn off from the apparatus at the same slow rate at which it is added, being taken both from the lowest layer, which contains lye, iodin, or acid, and from the uppermost layer, consisting, for instance, of a di- 5 luted solution of potassium chlorid containing chlorin or bromin. In order to avoid any agitation or'disturbance of the layers, the feed and outlet pipes are provided with sprayheads or a series of rose-like pipes within the siphons or the like.

When the process in a cell has been completed and it is required to stop working, the neutral zone may be allowed to decrease until it is almost on the point of vanishing, when a mechanical diaphragm may be introduced,

but this is only necessary when it is required to stop working one or more of the cells.

Av neutral zone or layer of the kind. de-

.decomposed solution forming the final small. neutral zone, siphons maybe introduced into the inlet-openings 0 0, through Whiclithe iupper part. of the solution standing in. the

chambers B and O andformingtheneutral' gzone may be removed, previous to drawingoff the pure products of theelectrolyticndecom position.

scribed is not formed by the processes hitherto employed, because the diffusion, or, more properly speaking, the endosmosis caused by the porous partition, gives rise to local currents which disturb the separating-layer and render itimpossible to obtain a concentration;

equalito that obtained by the present process.

Oneform of carrying out the present process is illustrated in the, accompanying dr'aw-- gof'ways, the formsillustrated anddescribed. ibeing merely instances.- fingbromidof sodium, as inall cases in which the products of decomposition. are heavier specifically than .theelectrolyte, the arrange ment: indicated in. Fig. 2 may be employed.

ings, forming part of this specification, and in which similar letters and figures of reference denote similar parts throughout the several views.

Figure 1 is a vertical cross-section through an apparatus which may be employed, and

Figs.v 2v and 3 are similar sections showing,

modifiedforms of the device.

The apparatusconsists of a receptacle having two impervious partitions W W'- extending across the same from about the top and reaching, down to ashort distance above the bottom and one partition W extending from the bottom upward and terminating some little distance below the top, said receptacle beingthus divided into four communicating compartments A, B, G, and D, through which theelectric current may flow from the, anode- N'to the cathode K withouthindrance.

The-two interior compartments B and 0' may be entirely separated one from the other by a'. slide E, so that the whole apparatusmay bedivided into two compartments A.B andC D, having no communication with each other. Such division would, however, only take place when the process of decomposition isto be stopped.

I will now proceed to give one, or two instances of the application of the process, the present-apparatus being employed.

If'bromid of sodium is subjected to the- 1 drawnoff at the cocks H and H. ess is to be stopped, the neutral zone should non-decomposed solution. While theprocess is being continued this separating-zone of non-decomposed solution willbe kept about constant by adding fresh solution to the neutral zone through the inlets 0' 0 in the same proportion as the decomposed solution is be allowed to decrease to a minimum and the slide E dropped just before the products of decomposition could mix over the partition In: order to remove the last traces of non- The process may be carriedout in a variety lhus .in electrolyz- In this case only two partitions W and W If the procare employed. The anode is. placedin the compartment or chamber. 3 at ortowarditheq bottom of. the same, the cathode iuthe cham her 1 near the surface of the liquid; The bromin collects inv chamber 3; andrises very.

slowly in the same.

The soda-lyeformed in:

chamber 1 sinks gradually to the bottom,

passesinto the; chamber 2, and rises in the same, the neutral zonebeing retained by addingsolution at the top of thechambersfl and 3 in thesame-proportion as-the decomposition, takes place, the. decomposedv products being drawnott. from the. lower. partsiof the.

This arrangement-of the.

chambers 1 and[3. cathodes allows the hydrogen toescapewithout crossing the electrolytic path, inwhich case it wouldagitate the solutionand cause If desired, one. of: the.

of indecomposed salt solutionzarrangedabove it, so thatthe formation of layerswill be present from the beginning.

If theproducts of decomposition resulting.

from the electrolysis are of different specific.

gravities, so that one productwould rise. and? the other sink, aswould be the case inelectrolyzin g potassiumchlorid andcyanid ofpotassium, in which case chlorin and cyanogen would escape as gases a-nd the potassium lye: sink to the bottom, or in electrolyzing rhod+ anid of potassium, in which case the specifically lighter sulfocyan'ic acid would rise and the potassium lye sink, the present process may be carried out in the manner shown at Fig. 3. In this case only one partition \V is employed. The potassium lye formed rises gradually in chambers 1 and 2. The separating-layer is formed by the layer of salt solution not yet decomposed and rising in the chamber 2. This layer or neutral zone may be isolated when it is required to stop the process by laterally sliding doors or partitions V V, and during the process fresh solution is conducted to the same by the inlet 0.

a a are two overflow-siphons for the correspondin g layers. The direction in which the layers increase is represented by arrows in all the figures.

Straight partitions are common to all the forms of apparatus for carrying out the process, as illustrated in Figs. 1 to 3, said partitions being vertically arranged and being impervious to the fluid and to the electric current. The partitions do not extend throughout the depth of the apparatus or of the liquid, but either begin below the level of the same or do not reach to the bottom. The distance at which the partitions are arranged from the bottom or from the level of the liquid must be so chosen as to prevent the lines of current from being narrowed at the points where the said current passes from one compartment of the apparatus to the next. The parallel partitions have the. effect that the section of the liquid remains constant at all points. A contraction of the lines of current would cause whirls and agitation of the liquid, which would disturb the formation of layers. Two points are of the greatest importance in order to retain the layers in their proper positions, viz: first, the entire omission of diaphragms of any description which might fill out the longitudinal or transverse section of a cell and enable the exchange of liquid from one cell to the other by endosmosis; second, the horizontal position of the electrodes with regard to each other and the arrangement of the same in difierent vertical planes. By this arrangement the gases rising from the electrodes are forced to pass through those columns of liquid only which do not form a conducting connection between the electrodes. Furthermore, this arrangement prevents any disturbance of the layers which could arise from the varying specific weights of the products of decomposition.

The'present process In ay be advantageously employed for treating all kinds of artificial and natural brine, for electrolyzing Stassfurt saline deposits, (the alkaline earths are precipitated in this case as hydroxids,) and generally for treating all kinds of soluble salts. The process further enables the production of acids, such as nitric acid, by electrolyziug saltpeter, sulfuric acid from sulfates, hy-

drochloric acid from an electrolyzed mixture of chlorids and sulfates by distillation.

If mineral anodes are employed, the minerals can be brought to solution by means of the present process.

The process may also be employed for purifying many substances and for separating out certain substances from mixtures, thus, for instance, for purifying iron or copper salts, waste 1 yes containing sulfid, syrups, as also for electrolyzing organic substances, in which the reducing or oxidating powers of the electric current are employed at one electrode.

I do not limit myself to the above specified decompositions, but intend to use this process in all kinds of electrolytical decompositions in which layers of difiering chemical consti-- tution are formed.

I claim as my invention 1. A process for electrolyzing chemical compounds and gaining the products of decomposition produced by the electrolysis which consists in filling an electrolytic cell, the passage of the current through which, from the anode to the cathode, is free from obstruction, by a-porous diaphragm with the salt solution to be decomposed, allowing the chemicallydifferent layers formed by the electrolysis to remain undisturbed and unaltered as long as the current is passing through the cell, then feeding fresh solution to the intermediate undecomposed layer of salt solution, which should be retained at a certain depth, and withdrawing the uppermost and lowermost layers of decomposed products at a point outsidethe influence of the path of the current,

in such proportion as to retain a predetermined position of the respective layers and at the close of the electrolysis dividing the layers by means of interposed partitions said partitions being mechanically impervious to the liquid substantially as described.

2. A process for electrolyzing chemical compounds, which consists. in first producing in an electric cell, the passage of the current through which, from the anode to the cathode is free from obstruction by a porous diaphragm, a layer of non-decomposed solution, passing an electric current through the cell and allowing a layer of the respective components into which the said solution is decomposed to form, one above and one below the said non-decomposed layer feeding fresh solution to the latter layer and withdrawing the decomposed anodic and cathodic solutions in such proportions as to retain approximately unaltered the layers formed by the electrolysis and finally at the close of the electrolysis substituting an actual mechanical partition for the non-decomposed layer, substantially as described.

3. The combination of a receptacle having a series of vertical partitions, arranged as regards the interior of the vessel or receptacle so as to allow the passage of the liquid above passing thecurrent to the electrodes substan-' or below the said partition-wal1s,horizontall'ytially as described. 1 disposed electrodes; arranged in different In witness whereof I have hereunto set my Vertical planes, afeed-pipe at a point between hand in presence of two Witnesses.

said electrodes for the fresh solution and out- WILLY BEIN. let-pipes above and below said electrodes for Witnesses: the decomposed layers said feed and outlet 'EUSTAOE HOPKINS,

pipes having spray-heads, and means for RICHARD -KAUTZ. 

